Vulcanization of rubber and new compound therefor



Patented Aug. 30, 1932 V A UNITEDTSTATES PATENTT OFFICE HUGH MILLS BUNBURY, 0F PRESTWIOH, JOHN sI'ANLEY HERBERT DAVIES, or" CRUMPSALL, AND WILLIAM JOHNSON SMITH NAUN'roN, or PRES'IWICH, ENGLAND, ASSIGNORS T0 IMPERIAL CHEMICAL IND STRIES LIMITED, a oonronATIoit'oF.

oiaEAT' BRITAIN VULCANIZATION OF RUBBER AND NEW COMPOUND THEREFOR No Drawing. Application filed October 28, 1931, Serial No. 571,678, and in'G'reatBr itain November 3', 19 30.

This invention relates to the vulcanization of rubber and rubber-like substances and in particular to the use, as accelerators of vulcanization, of a new group of substances as hereinafter described; a

According to the invention we eifect vulcanization of rubber and'rubber-like substances in the presence of a compound having the general formula N=O-X--N z-t =Nd-Y wherein X represents a substituted amino group, Y and Z represent Q-mercapto-arylenethiozole residues,

N Ar o-sp v (Ar being an ortho arylene radical). I

By the process of our invention vulcanization takes place smoothly and eifective'ly at an appropriate temperature,e. g. 140 6., whereas at lower temperature, e. g. up to 100 little or no vulcanization takes place. We thus avoid scorching, i. e. premature vulcanization during milling, mixing and calendering. Our new accelerators may thus be described as exhibiting the property of delayed action.

The improvements resulting from our new process are favourably displayed when our new acceleratorsare applied in conjunction with a basic accelerator, e. g. diphenyl-guanidine.

Compounds having the above general for mula, may bemade by effecting interaction between cyanuric chloride and one molecular proportion of a primary arylamine (compare, e. g. Fries, Berichte, 1886, 19, 2056), followed by condensation with two molecular PIOPOI": tions of an alkali salt of a 2-mercaptoarylenethiazole, or by condensing cyanuric chloride first with two molecular proportions of a 2-mercaptoarylenethiazole (preferably, .as alkalisalt) and then with a primary aryl: amine. Thus Fries primary B-naphthylamino-cyanur'ic chloride is obtained. by treating cyan l ic chloride with two; mo.-

' lecular proportions of ,B-naphthyl amine. This compound is heated inacetone solution with two molecular proportions of the sodium salt of 2mercaptobenzth1azole to give one of'our new vulcanization accelerates.

The invention is illustrated but not limited 'by the followingexamples, in which the. parts are by weight.

' Ewample l p v 6.2 parts of the sodium saltof mercapto benzthiazole are dissolved in 50 parts .of

acetone, and the solution obtained is added withstirring to a solution of 5.3 parts of the interaction product of one molecular proportion of cyanuric chloride and two mole'cular proportions of ,B naphthyIamine prepared as described by Fries (Berichte, 1856,19, 2056 in35 parts of acetone. The mixture is boiled pound is removed by filtration, washed with waterand dried. It has a] melting pointof 18&1S9 C. H i i 0.25 part of the new compound are mixed with 0.25 part of diphenylguanidiiie and under, reflux and a heavy white precipitate is formed. 'After cooling the separated com? a tensile strength at break of only 8.4 kg. perv 7 sq. cm. The percentage elongations at break are 788 and 800, respectively.

p Example if H In this example there are used compounds of the formula i i V ourn o-s-t=N- i-sf ouL f V s/ \S/ i (where R is phenyl, o-tolyl, .or p-t olyl) obtained either by a processsimilar to that de- 7 scribed above oras follows 9.2 parts of finely divided cyanuric chloride are dissolved in 1 1 parts'of benzene. solution is thencooled to 10 C. and well- The New compound Cured 20 minutes Cured minutes at 141 0. at 110 C.

New compound iised Tensile Tensile V V strength zgg g strength Eg at break tiong t at break tiongat in kg. per b i in kg. per b sq. cm. sq. cm.

Ani1inb-compound i 144 793 is. o "651 o Tolui'dino-compound 154 750 :15. 7' 724 p-Toluidino-con pound 140 750 8. 7 693' one molecularproportion of a primary-arm; mat c amine and two molecular proportions I 'Barytes i Zinc mnde stirred. 9.3 parts of aniline dissolved in 44 parts of benzene are quickly added. During this reaction the temperature rises to about 5060 0. Continued stirring and cool,- ing soon-reduces the temperature to about 20 C. and stirring at this temperature is continued for about A; hour. The aniline hydrochloride which separates'as a white precipitate isthen filtered off and washed with a further quantity of benzene. the sodium salt of me'rcapto-benzthiazole are well powdered and added to the combined benzene filtrates, and the mixture is stirred and boiled under refiux'for about five hours; After the reaction is complete, the mixture is "cooled and'filtercd.

i The solid'materialis washed with dilute aqueous caustic soda until alkali soluble Ina-- terial is removed, then washedwith water and dried; 1 It isa whitepowder, soluble in toluene, in. p. about 176181 C. Y r

The product obtained .by using 10.7- parts of o-toluidine instead 0159.3 parts ofaniline has m. p. about 126 (3., and that obtained similarly but using 10.8 parts of has m. p. 185190 C. V V

A rubber mix composed as follows 1 a1e crepe rubber I Su1phur Diphenylguanidine is made up and vulcanized at the usual vulcanizing temperature, viz. 141 C. In order to demonstrate that vulcanization does not proceed at a lower temperature, a test is also carried out at 110, C. v The fOHOWlIlglESllltS are obtained V Since many embodiments of this invention, differing widely in one or more respects, may be 1 made without departing from the spirit ofrour invention, it is to be understood that we do not limitourselves to the foregoing examples or description except as indicated in the followingclaims. a

W e claim:

1. Theprocess of producing a new cheniical compound which is an effective accelerator for the vulcanization of rubber, which comprises condensing cyanuric chloride with of a 2-mercaptoarylenethiazole."'

189 parts of captoarylenethiazole.

p-toluidine 2. The process of producing a new chemical compound which is an effective accelerator for the vulcanization of rubber, which comprises condensing cyanuric chloride with one molecular proportion of a primary aromatic amine and two molecular proportions of an. alkali metal salt oia,2-mercaptoarylencthi'azole: f 8. The process of producing a new chem- V ical compound which is an efl'ective accelerator for the vulcanization of rubber, which comprises condensing a primary arylamino cyanuric chloride with'two molecular proportions of a Q -inercaptoarylenethiazole. H

4:. The process of producing a new chemical compound which is an effective accelerator for the vulcanization of rubber, which comprises condensing a primary arylaniiiiocyanuric chloride with two molecular. proportions of an alkali metal salt ofa 2-mer- 5. A new chemical compound siiitable for use as an accelerator in-theivulcanization of rubber, which possesses the probable .formula:

=.Q,X Z,(E=N EI.Y wherein X represents an arylamino-group,

andY and Z represent Q-mercaptoarylenethL produced by the process oi claim 2, preferably in the'presence of a basic organicac celerator. I i

8. The process of vulcanizing rubber or rubber-like substances, which consists in adding to the mix'a' vulcanization accelerator produced by the process of claim 3, prefer ably in the presence of a basic organic-ac celerator. p 7 v V 9. The process ofvulcanizing rubber'or rubber-like substances,wliich consists in adding to the mix a vulcanization accelerator produced by the process of claim 4, preferably the presence erator. 5 t ,7 v V 10. The process oif vulcanizingrubber or f eb c o is niqa 'r rubber-like substances, which consists in addmg to the mix a vulcanization accelerator ob tainable by the process of .ClfilIIl'l, preferably in the presence of diplienylguanidine.

11; The c process of 1 vulcanizing rubber or rubber-like substances-which consists in add ing to the mix a vulcanization accelerator obtainable by the process of claim 2, preferably in the presence of diphenylguanidine.

12. The process of vulcanizing rubber or rubber-like substances, which consists in adding to the mix a vulcanization accelerator obtainable by the process of claim 3, preferably in the presence of diphenylguanidine.

13. The process of vulcanizing rubber or rubber-like substances, which consists in adding to the mix a vulcanization accelerator obtainable by the process of claim 4, preferably in the presence of diphenylguanidine.

14. The process of producing a new chemical compound which comprises condensing cyanuric chloride with one molecular proportion of a primary aromatic amine of the group consisting of aniline, o-toluidine and p-toluidine and two molecular proportions of an alkali metal salt of a 2-mercaptoarylenethiazole.

15. The process of producing a new chemical compound which comprises condensing cyanuric chloride with one molecular proportion of a primary aromatic amine of the group consisting of aniline, o-toluidine and p-toluidine and two molecular proportions of an alkali metal salt of a 2-mercaptobenzthiazole. V

16. The process of producing a new chemical compound which comprises condensing cyanuric chloride with two molecular proportions of B-naphthylamine and two molecular proportions of an alkali metal salt of a 2-mercaptoarylenethiazole. x 17. The process of producing a new chemical compound which comprises condensing cyanuric chloride with two molecular propor tions of B-naphthylamine and two molecular proportions of an alkali metal salt of a 2-mercaptobenzthiazole.

18. A new chemical compound obtainable by condensing cyanuric chloride with at least one molecular proportion of an amine of the group consisting of B-naphthylamine, aniline, o-toluidine, and p-toluidine and two molecular proportions of an alkali metal salt of a 2-mercaptoarylenethiazole.

19. A new chemical compound obtainable by condensing cyanuric chloride with at least one molecular proportion of an amine of the group consisting-of B-naphthylamine, aniline, o-toluidine and p-toluidine and two molecular proportions of an alkali metal salt of a 2-mercaptobenzthiazole.

20. The process of vulcanizing rubber or rubber-like substances, which comprises adding to the mix a vulcanization accelerator obtainable by the process of claim 14;, and a basic organic accelerator such as diphenylguanidine, and then subjecting the mix to vulcanizing conditions.

21. The process of vulcanizing rubber or rubber-like substances, which comprises adding to the mix a vulcanization accelerator obtainable by the process of claim 15, and a basic organic accelerator such as diphenylguanidine, and then subjecting the mix to vulcanizing conditions.

22. The process of vulcanizing rubber or rubber-like substances, which comprises adding to the mix a vulcanization accelerator obtainable by the process of claim 16, and a a Iii-testimony whereof we have aflixed our signatures.

HUGH MILL? BUNBURY. JOHN STANLEY HERBERT DAVIES. WILLIAM JOHN. SMITH NAUNTON. 

